A Simple Link between Hydrocarbon and Borohydride Chemistries

Poater, Jordi; Solà, Miquel; Viñas, Clara; Teixidor, Francesç

doi:10.1002/chem.201204397

Cited by 48 publications

(36 citation statements)

References 60 publications

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“…Hexasilabenzene has a nonplanar equilibrium structure with D 3 d symmetry, which is completely different from the planar D 6 h structure of benzene. To investigate the tendency for the planarity of the analogues, we conducted a survey of the structures of various cyclic 6π isovalent compounds with benzene, classified into five categories: (1) X 6 H 6 (X: group 14 elements); (2) X 3 Z 3 H 6 (X, Z: group 14 elements in different periods); (3) X 3 Z 3 H 6 (X: group 13 elements, Z: group 15 elements); (4) [X 3 Z 3 H 6 ] 3− (X: group 13 elements, Z: group 14 elements); and (5) [X 3 Z 3 H 6 ] 3+ (X: group 14 elements, Z: group 15 elements), as shown in Table , Figure and Supporting Information Tables S1–S3.…”

Section: Resultsmentioning

confidence: 99%

The planarity of heteroatom analogues of benzene: Energy component analysis and the planarization of hexasilabenzene

Nakamura

Kudo

2018

J Comput Chem

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There are various nonplanar heteroatom analogues of benzene—cyclic 6π electron systems—and among them, hexasilabenzene (Si6H6) is well known as a typical example. To determine the factors that control their planarity, quantum chemical calculations and an energy component analysis were performed. The results show that the energy components mainly controlling the planarity of benzene and hexasilabenzene are different. For hexasilabenzene, electron repulsion energy was found to be significantly important for the planarity. The application of the pseudo Jahn–Teller effect and the Carter–Goddard–Malrieu–Trinquier model for the interpretation of the planarity of the benzene analogues was also investigated. Furthermore, based on the quantitative results, it was revealed that the planarization of hexasilabenzene is realized by introducing substituents with π‐accepting ability, such as the boryl group, that bring about a reduction of the π‐electron repulsion on the silicon skeleton. © 2018 Wiley Periodicals, Inc.

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Section: Resultsmentioning

confidence: 99%

The planarity of heteroatom analogues of benzene: Energy component analysis and the planarization of hexasilabenzene

Nakamura

Kudo

2018

J Comput Chem

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“…In previous works, together with Poater, Viñas, and Teixidor, we established a connection between the Hückel rule for 2D classical aromaticity and the Wade–Mingos rule for 3D aromaticity in closo BHs. To reach this objective, we first established a link between hydrocarbons and boronhydrides applying the so‐called electronic confined space analogy (ECSA) method . The steps followed in the ECSA method are the following: (a) we state the model organic hydrocarbon compound; (b) we transmute each C atom into a B atom and one electron ( eT ); (c) these extra electrons are replaced by sacrificial atoms ( sA ); (d) and finally (if necessary) we generate the new boronhydride compound by structural relaxation ( sR ).…”

Section: Connecting Rulesmentioning

confidence: 99%

Connecting and combining rules of aromaticity. Towards a unified theory of aromaticity

Solà

2018

WIREs Comput Mol Sci

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Most of the archetypal aromatic compounds present high symmetry and have degenerate highest‐occupied molecular orbitals. These orbitals can be fully occupied resulting in a closed‐shell structure or can be same‐spin half‐filled. This closed‐shell or same‐spin half‐filled electronic structure provides an extra stabilization and it is the origin of several rules of aromaticity such as the Hückel 4N + 2 rule, the lowest‐lying triplet excited state 4N Baird rule, the 4N rule in Möbius‐type conformation, the 4N + 2 Wade–Mingos rule in closo boranes or the 2(N + 1)2 Hirsch rule in spherical aromatic species. Combinations of some of these rules of aromaticity can be found in some particular species. Examples of these combinations will be discussed and the validity of some of these rules will be assessed. Moreover, it is possible to establish connections with some of these rules of (anti)aromaticity and, therefore, they can be partially generalized, which represents a step forward to a future unified theory of aromaticity. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Electronic Structure Theory > Density Functional Theory Software > Quantum Chemistry

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“…We established14 a link between the hydrocarbon and borohydride chemistries by showing that HCs and BHs have a common root regulated by the number of VEs in a confined space. Herein, we go one step further by applying the electronic confined space analogy (ECSA) method to bridge fundamental aromatic HCs and the analogous closo BH clusters.…”

Section: Calculated Nics Values [Ppm] and Bond Length Alternation δR mentioning

confidence: 99%

π Aromaticity and Three‐Dimensional Aromaticity: Two sides of the Same Coin?

et al. 2014

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A bridge between classical organic polycyclic aromatic hydrocarbons (PAH) and closo borohydride clusters is established by showing that they share a common origin regulated by the number of valence electrons in an electronic confined space. Application of the proposed electronic confined space analogy (ECSA) method to archetypal PAHs leads to the conclusion that the 4n+2 Wade–Mingos rule for three‐dimensional closo boranes is equivalent to the (4n+2)π Hückel rule for two‐dimensional PAHs. More importantly, use of ECSA allows design of new interesting fused closo boranes which can be a source of inspiration for synthetic chemists.

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A Simple Link between Hydrocarbon and Borohydride Chemistries

Cited by 48 publications

References 60 publications

The planarity of heteroatom analogues of benzene: Energy component analysis and the planarization of hexasilabenzene

The planarity of heteroatom analogues of benzene: Energy component analysis and the planarization of hexasilabenzene

Connecting and combining rules of aromaticity. Towards a unified theory of aromaticity

π Aromaticity and Three‐Dimensional Aromaticity: Two sides of the Same Coin?

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